CN108699209A - The method for being used to prepare polyurethane foam - Google Patents
The method for being used to prepare polyurethane foam Download PDFInfo
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- CN108699209A CN108699209A CN201780014974.7A CN201780014974A CN108699209A CN 108699209 A CN108699209 A CN 108699209A CN 201780014974 A CN201780014974 A CN 201780014974A CN 108699209 A CN108699209 A CN 108699209A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5006—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms
- C08G18/5012—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms having bromine atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0019—Use of organic additives halogenated
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2207/00—Foams characterised by their intended use
- C08J2207/04—Aerosol, e.g. polyurethane foam spray
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
- C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to:The method for being used to prepare polyurethane foam, these methods include the steps that the compound wherein with low granularity discharges chemistry and/or physical blowing agent by decomposing;The polyurethane foam that is prepared by such method and comprising at least one polyalcohol and with low granularity, the composition of the compound of chemistry and/or physical blowing agent and the purposes of such composition can be discharged by the degradation of thermal induction and/or chemical induction.
Description
The present invention relates to:The method for being used to prepare polyurethane foam, these methods include the chemical combination for wherein having low granularity
The step of object is by decomposing to discharge chemistry and/or physical blowing agent;The polyurethane foam and packet prepared by such method
Containing at least one polyalcohol and with low granularity, can by the degradation of thermal induction and/or chemical induction come discharge chemistry and/or
The composition of the compound of physical blowing agent and the purposes of such composition.
Polyurethane foam can be by keeping suitable polyisocyanate (usually more with isocyanates-reactive compounds
First alcohol) mixture reacted in the presence of a blowing agent to prepare.This class A foam A is typically used as insulation medium.These insulative properties
Depending on many factors, including abscess-size.The heat barrier foam for the abscess-size for having small has been proposed in the prior art.
Theoretically, the small abscess-size in nanometer range should generate excellent insulative properties, because gas can to the contribution of thermal conductivity
It can be lowered (' Knudsen effect ').For this purpose, 9139683 B2 of US suggest using overcritical or near-critical CO2As foaming
Agent.However, overcritical or near-critical processing is not direct and may constitute risk to employment security.
Therefore now, the invention enables the polyurethane foam of improved polyurethane or modification and it is used to prepare (modified)
The improved method of polyurethane foam is available.The object of the present invention is to provide a kind of safer, more economical and/or more ecological
Method.Moreover, it is an object that a kind of method, this method is generated with improved stability, combustibility, heat-insulated
The polyurethane foam of characteristic, machinability, and/or abscess-size.
This purpose and other purposes are being realized through the invention as summarized in patent claims.
Therefore, one aspect of the present invention is related to a kind of side for the polyurethane foam being used to prepare polyurethane foam or modification
Method, this method include that wherein compound discharges chemistry and/or physical blowing agent by the decomposition of thermal induction and/or chemical induction
The step of, wherein the compound, which has, is equal to or less than 1 μm, is preferably equal to or lower than 500nm, is more preferably equal to or less than
The size distribution for being expressed as D50 of 250nm.
Polyurethane foam is typically to be prepared by making two kinds of individual composition contacts.On the one hand, the so-called sides B-
(B-side), it is usually made of the mixture of isocyanates or isocyanates.On the other hand, the so-called sides A- (A-side) packet
It is contained in the every other component used in the production of foam, especially polyalcohol or polyol blends.The sides A- and the sides B-
This Europe that is defined on be widely used and also use herein.The sides A- generally further include foaming agent, fire retardant, catalyst,
Surfactant and other auxiliary agents.In a preferred embodiment, which is prepared by spraying foaming.Injection
It foams and means that the sides A- and the sides B- is made to combine in nozzle under stress and be then applied directly to need heat-insulated space, such as
Wall, roof or construction set.
Foaming agent is the compound that foam structure or matrix can be produced during polyurethane foam is formed.
Chemical foaming agent is known in the art.Term " chemical foaming agent " is intended to indicate that and in frostproof froth n process
The foaming agent that at least one component of the middle composition used is chemically reacted.More specifically, due to water with isocyanates
Reaction in form CO2, may be used as chemical foaming agent.The CO being consequently formed2It is used to generate foam structure in the foam.
To avoid doubt, term " chemical foaming agent " as used herein from being intended to the chemistry for meaning to be formed in the decomposition reaction of compound
Foaming agent.
Physical blowing agent is also known in the art.Term " physical blowing agent " be intended to indicate that usually not in foam
The foaming agent that one of component of composition used in foaming process is chemically reacted.Suitable physical blowing agent includes dioxy
Change carbon, carbon monoxide, nitrogen and hydrogen.Specifically, carbon dioxide is used as physical blowing agent.To avoid doubt, such as herein
The term " physical blowing agent " used is intended to the physical blowing agent for meaning to be formed in the decomposition reaction of compound.
Term " polyurethane foam " is intended to indicate that the polymer for reacting generation substantially by polyalcohol and isocyanates.This
A little polymer are typically by showing that the preparation from 100 to 180 isocyanate index obtains.Term " modified poly- ammonia
Ester foam " is intended to indicate that, by the polymer generated that reacts of polyalcohol and isocyanates, these isocyanates include in addition to amino
Other kinds of functional group except formic acid esters functional group, the three isocyanide urea rings formed especially by the trimerization of isocyanates
(triisocyanuric ring).These polyurethane being modified are commonly known as poly-isocyanurate (PIR).These polymer
Typically by showing that the preparation from 180 to 550 isocyanate index obtains.
Preferably, polyurethane foam and modified polyurethane foam be rigid, closed-cell foam.
Any isocyanates for being routinely used for manufacturing this class A foam A can be used in the method according to the invention.Example
Such as, it can be mentioned that aliphatic isocyanates (such as hexamethylene diisocyanate) and aromatic isocyanate (such as toluene two is different
Cyanate or methyl diphenylene diisocyanate).
Any polyalcohol for being routinely used for manufacturing this class A foam A can be used in the method according to the invention.Term
" polyalcohol " is intended to indicate that the compound for including more than one hydroxyl in the structure, such as the compound may include 2,3 or 4
Hydroxyl, further preferably 5 or 6 hydroxyls;And it is intended to the polyalcohol comprising the chemical constitution with single restriction and with difference
The mixture of the polyalcohol of chemical constitution.The polyalcohol preferably synthesized.Further preferably polymerized polyalcohol, more preferable polyester
Polyalcohol or polyether polyol.The suitable example of polyester polyol includes polycaprolactone glycol and diethylene glycol terephthalic acid (TPA)
Ester.The suitable example of polyether polyol includes polyethylene glycol (such as PEG 400), polypropylene glycol and poly- (tetramethylene ether) two
Alcohol.Polyether polyol further preferably based on carbohydrate, glycerine or amine.The example packet on suitable carbohydrate basis
Include sucrose and D-sorbite.Most preferably brominated polyetherdiol, such as polyether polyol B350 (No. CAS:68441-62-
3).Especially suitable for the mixture of polyether polyol B 350 and triethyl phosphate, can exist from Su Wei groups (Solvay)
Brand name251 times acquisitions of B.
It is optionally possible to by selected from fire retardant, foam stabiliser, catalyst, surfactant and co-foaming agent at least
A kind of other component is added to the sides B- or is preferably added to the sides A-.
The co-foaming agent can be selected from chemistry and/or physical blowing agent as described above.
" the chemical co-foaming agent " being such as used in the present invention is intended to indicate that included in the sides A- can be with the isocyanide of the sides B-
The component of acid esters reaction.It is believed that the energy discharged in the form of heat from this reaction promotes further foam manufacture process.
Preferred chemistry co-foaming agent includes water, NH3, primary amine, secondary amine, alcohol (preferably difunctional alcohol or trifunctional alcohol), azanol and ammonia
Base alcohol.Especially preferably bifunctional amine or polyfunctional amine, glycol or glycerine.Suitable example includes diaminoethanes, 1,
3- diaminopropanes and triethanolamine.
Preferred physics co-foaming agent includes alkane, such as propane or cyclopropane, alkyl fluoride (HFC) and fluorinated olefins
(HFO).About HFC and HFO, for example, it can be mentioned that 1,1,1,3,3- 3-pentafluorobutane (HFC 365mfc), 1,1,1,2- tetrafluoro second
Alkane (HFC-134a), 1,1,1,2,3,3,3- heptafluoro-propanes (HFC 227ea), 1,1,1,3,3- pentafluoropropanes (HFC 245fa),
The mixture of alkenyl halide (as HFO-1234yf, HFO-1234zr and HFO-1233zd) or the alkane and alkene.
If using co-foaming agent, preferably extremely with total weight 1wt% to 20wt%, more preferable 2wt% based on the sides A-
The range of 10wt%, most preferably 3wt% to 7wt% use.
Conventional use of any fire retardant in the manufacture of this class A foam A can be used.For example, it can be mentioned that being based on phosphorous
The fire retardant of acid esters.Suitable example includes triethyl phosphate (TEP), three (2- chloro isopropyls) phosphates (TCPP), dimethyl
Propane phosphonic acid ester (DMPP), diethyl ethane phosphonate ester (DEEP), triethyl phosphate, phosphoric acid trichlorine isopropyl ester.In fact, being made
The amount of fire retardant be generally every 100 weight polyol from about 0.05 to 50 parts by weight, preferably 1 to 25 parts by weight,
More preferable 10 to 20 parts by weight variation.
Suitable catalyst includes catalysis by reacting formation-NH-CO-O- amino first between polyalcohol and isocyanates
The compound reacted between acid esters key or activation isocyanates and water, such as tertiary amine and organotin, iron, mercury or lead compound.
It particularly can be mentioned that triethylamine, N, N- dimethyl cyclohexyl amines, N-methylmorpholine, N-ethylmorpholine, dimethyl second as tertiary amine
Hydramine, Er Danza [2.2.2]Double-octane (triethylenediamine) and the benzylamine of substitution, such as N, N- dimethyl benzylamines and N,
N, N ', N ", N "-five methyl diethylentriamine (PMDTA).As organotin or lead compound, particularly it can be mentioned that February
Dilaurylate, stannous octoate and lead octoate.It is intended for modified polyurethane (poly-isocyanurate) foam of manufacture
Other suitable catalyst include the compound for being catalyzed isocyanates to the trimerization of three isocyanuric acid esters.
In fact, the amount of used catalyst is generally every 100 weight polyol from about 0.05 to 10 weight
Part variation.Generally, the amount of composition according to the present invention is every 100 weight polyol from 1 to 80 parts by weight.It is preferably
It is every 100 weight polyol from 10 to 60 parts by weight.
Conventional use of any foam stabiliser in the manufacture of this class A foam A can be used.For example, it can be mentioned that silica
Alkane copolyether.In fact, the amount of used foam stabiliser is generally the polyalcohol of every 100 parts by weight from about
0.05 to 10 parts by weight, preferably 0.5 to 3.0 parts by weight, the variation of more preferable 1 to 2 parts by weight.
Term " decomposition of thermal induction " is intended to indicate that the decomposition of compound, is mainly exposed to raised temperature by by compound
The influence of degree.Preferably, which is involved heat-producing chemical reaction in the formation of foam as a result, for example different
The result of cyanate and polyol reaction.It is further preferred that the raised temperature is supplied by extra power, more preferably by by A-
Side or the sides B- component or any or all of the device used in foaming process preheat to supply." raised temperature "
It is intended to indicate that the temperature higher than environment temperature.Suitable temperature is from 30 DEG C to 100 DEG C, preferably from 40 DEG C to 90 DEG C, more preferably
From 50 DEG C to 80 DEG C.The specific example of the decomposition of thermal induction is sodium bicarbonate (NaHCO3) decomposition.In this case, the liter
High temperature is above the decomposition temperature (50 DEG C) of sodium bicarbonate.
Preferably, compound discharges chemistry and/or physical blowing agent by the decomposition of thermal induction.It is highly preferred that the change
Close object there is no under acidic activator by the decomposition of thermal induction come discharge chemistry and/or physical blowing agent.Preferred real
It applies in example, the sides A- or the sides B- or both the sides A- and the sides B- can be preheated before producing foam.They can be preheated to
Temperature from 25 DEG C to about 80 DEG C, preferably from 30 DEG C to 60 DEG C, more preferably from 40 DEG C to 50 DEG C.The preheating step can be
Including being carried out in the storage tank of the sides A- and/or the sides B-.It can also in the pipeline from storage tank to the mixing point of the sides A- and the sides B- into
Row.The mixing head that is used in mixed way routinely carries out.Alternatively, can heat the mixing head itself with just mixing step it
The preceding sides preheating A- and/or the sides B-.If carrying out foam production by spraying foam process, the nozzle itself can be heated.
Term " decomposition of chemical induction " is intended to indicate that the decomposition of compound, mainly by the compound and activator, excellent
Choosing and alkalinity or the influence of acidic activator chemical reaction.Suitable acidic activator includes bronsted acid, such as carboxylic acid, spy
It is not citric acid, acidic acid and formic acid.It is further preferred that the acidic activator can be formed in situ during foaming process.It is suitble to
Example be can be by reacting the acetic acid being formed in situ from acid anhydrides with water.In a more preferred embodiment, NaHCO3With acid anhydrides
It is applied in combination.
Preferably, more preferably in the presence of acidic activator, most preferably in citric acid, acetic acid, polyphosphoric acid and/or formic acid
In the presence of, which discharges chemistry and/or physical blowing agent by the decomposition of chemical induction.It is further preferred that the acid is living
Agent is dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid or adipic acid.The acid activators are preferably included in the sides A-
In.In another preferred embodiment of injection foaming, by the acid activators via third pipe during spraying foaming process
Line is added to nozzle simultaneously.
It is further preferred that the compound discharges chemically and physically both foaming agents.It is highly preferred that the compound passes through thermal induction
Decomposition discharge chemically and physically both foaming agents.
Preferably, which is inorganic carbonate.Suitable inorganic carbonate includes NaHCO3,Na2CO3,CaCO3,
(NH4)2CO3,NH4HCO3,MgCO3And trona.In the specific embodiment of the present invention, which is NaHCO3。
It is further preferred that the compound is the hydrate of the hydrate of inorganic salts, more preferable alkali metal salt or alkali salt,
Most preferably the compound is the hydrate of sodium sulphate, especially Na2SO4·10H2O。
Preferably, which has equal to or more than 10nm, preferably equal to or greater than 50nm, more preferably equal to or greater than
The size distribution for being expressed as D50 of 100nm.It is further preferred that the size distribution for being expressed as D50 be equal to or higher than 1nm, preferably etc.
In or higher than 10nm.More preferably from 25nm to 250nm, most preferably between 50nm and 150nm.Specifically, from 60nm to
100nm。
Size distribution according to the present invention is provided with D50 values, it means that the 50% of sample quality is by less than given value
Particle is constituted.The size distribution can use laser diffraction particle size analyzer (BeckmannLS 230) it measures.
Sample is added in the instrument, is in the instrument added to the sample in isopropanol medium at room temperature.
Compound with the size distribution in the scope of the invention is commercially available.Alternatively, for example, they can lead to
The controlled precipitation from suitable starting material is crossed to prepare.For example, the NaHCO with suitable size distribution3It can be by adding
Add ammonium hydrogen carbonate to precipitate, filter from the saturated solution of sodium chloride and collects.
Compound with the size distribution in the scope of the invention can also be prepared by reducing the granularity of compound.It is excellent
The reduction of selection of land, this granularity carries out in grinder.Particularly suitable grinder is ball mill, also referred to as planetary grinding
Machine, ball mill or pearl grinding machine.Therefore, by loose solid mill medium stirred together with the compound with realize grinding and/
Or milling efficiency.Compatibly, which mills medium including being for example made of flint, steel, glass or ceramics (such as zirconium oxide)
Hard object.The shape of the medium of milling can change and can be for example selected from sphere, ovoid, polyhedron or torus.
What sphere was especially suitable for.In the case of sphere, the size for medium of milling is from 0.01mm to 1.00mm, preferably in 0.03mm
To between 0.10mm, more preferably from about 0.05mm.
The granularity of the compound can also be reduced by being co-mulled and made into.Therefore, the compound is made (preferably to have in agent of milling altogether
Have the agent of milling altogether than the compound bigger hardness) in the presence of be subjected to grinding steps.Term " hardness " is referred to according to Mohs
The hardness of scale (Mohs scale).The suitable example of agent of milling altogether includes silica, sand, zeolite and metal (preferably alkali
Metal or alkaline-earth metal) oxide, such as CeO2,ZrO2, MgO or ZnO.Being co-mulled and made into can drape over one's shoulders according in such as US 5466470
The program of dew carries out.This is co-mulled and made into agent and preferably can also be the compound that can discharge chemistry and/or physical blowing agent.
In suitable example, NaHCO can be co-mulled and made into3And NaSO4·10H2The mixture of O.This is co-mulled and made into step most preferably in ball milling
It is carried out in machine.
It is further preferred that after at least one component that compound is suspended in the sides the B- sides Zhong HuoB-, such as be suspended in
After in the mixture of the isocyanates or isocyanates that are used during frostproof froth n, the granularity of the compound can be reduced.
It is highly preferred that after at least one component that compound is suspended in the sides the A- sides Zhong HuoA-, such as it is suspended in frostproof froth n
After in at least one polyalcohol used in the process, the granularity of the compound can be reduced.It is further preferred that being hanged by compound
After floating at least one fire retardant, such as after being suspended in triethyl phosphate and/or phosphoric acid trichlorine isopropyl ester, it can subtract
The granularity of the small compound.Therefore, which is a kind of method, and this approach includes the following steps:
A1) preparation includes the suspension of or mixtures thereof the compound and at least one polyalcohol or at least one fire retardant
Liquid,
A2) make in step a1) in formed the suspension reduce the size distribution of the compound through being subject to processing, and
B) make in step a2) in formed the suspension contacted with the composition comprising at least one isocyanates to prepare
Polyurethane foam, wherein compound discharge chemistry and/or physical blowing agent and the wherein chemical combination under heat and/or chemical activation
Object has the size distribution for being expressed as D50 equal to or less than 1 μm.
Preferably, the processing of the reduction size distribution includes grinding steps, more preferably uses the grinding steps of ball mill.
It is further preferred that the processing of the reduction size distribution includes sonication step.
It is further preferred that the processing of the reduction size distribution includes grinding simultaneously and sonication step.
In another preferred embodiment according to the method for the present invention, the compound (especially NaHCO3) granularity
Reduced by being ground in abrasive solvents.Term " abrasive solvents " is intended to indicate that solvent, and compound is subjected to grinding in the solvent
Step is ground, and the abrasive solvents are removed before the compound is used for foam production.The boiling point of the abrasive solvents is excellent
Selection of land is between 50 DEG C and 150 DEG C, more preferably between 60 DEG C and 120 DEG C.The example of suitable abrasive solvents include alcohol,
Water, hydrocarbon, hydrofluorocarbons and chlorinated hydrocabon.Preferably, which is ethyl alcohol, propyl alcohol, isopropanol, isobutanol.Grinding further preferably
Solvent is perfluoropolyether, especially from Solvay Fluor & Derivate (Solvay Fluor GmbH)Product system
Row, especiallyHT55。
The compound (especially NaHCO3) concentration in the abrasive solvents is between 10wt% and 70wt%, preferably
Ground 20wt% to 50wt% and more preferably between 30wt% and 40wt%.
In a preferred embodiment, which carries out in the presence of surfactant.It is without being bound by theory, it is believed that
The surfactant avoids the reunion and/or aggregation of the compound.
" surfactant " should indicate amphiphilic organic cpd, it is intended that these organic compounds simultaneously comprising hydrophobic group and
Hydrophilic group.
The example of suitable nonionic surfactant includes but not limited to the alcohol ethoxylate of straight chain, polyoxyethylene alkane
Base phenol ethoxylate, polyoxyethylene alcohol ethoxylate, polyoxyethylene carboxylate, polyoxyethylene alkyl amine, the more Portugals of alkyl
Glucosides, ethylene oxide-propylene oxide copolymer or combinations thereof.
The example of suitable cationic surfactant include but not limited to quaternary ammonium salt, ethoxylation quaternary ammonium salt or its
Combination.Preferred cationic surfactant can be with the carbon chain lengths of 8-20 carbon atom.
It is preferred that having the surfactant of phosphate, carboxylate, sulfonate or sulfate group as hydrophilic group.Further preferably
Be the surfactant that there is polyethers or polyester base side chain as hydrophobic group.Preferred polyethers base side chain have 3 to 50, it is excellent
Select 3 to 40, particularly 3 to 30 alkylene oxide groups.The alkylene oxide group be preferably chosen from by methylene oxygroup, ethyleneoxy group,
The group of propylidene oxygroup and butylidene oxygroup composition.The length of the polyethers base side chain generally from 3nm to 100nm, preferably from
10nm to 80nm.
The suitable example of such surfactant indicates by phosphoric acid derivatives, an oxygen atom of wherein P (O) group
Replaced by C3-C10 alkyl groups or alkenyl group.
The surfactant can be such as di-phosphate ester with polyethers or polyester base side chain and alkenyl part.With 4
Alkenyl to 12, particularly 4 to 6 carbon atoms is that height is suitble to.The particularly preferably phosphorus with polyether/polyester side chain
Acid esters, the phosphate ester salt with polyethers/alkyl side chain and the surfactant with deflocculated effect are (based on for example with adding
The high molecular weight copolymer of the group of work pigment compatibility).
The abrasive solvents are removed after the grinding steps and prepare at least one of the compound in the sides A- or in the sides A-
Suspension in component carries out suspension media exchange.This exchange can be carried out by conventional means, such as be steamed using rotation
Send out device.
According to this preferred embodiment, the processing for reducing size distribution includes the following steps:
M1 the compound (especially NaHCO) is prepared3) suspension in abrasive solvents,
M2) make in step m1) in formed the suspension reduce the size distribution of the compound through being subject to processing, especially
Grinding steps,
M3 the abrasive solvents) are removed by evaporating and/or filtering,
M4) prepare in step m3) in formed the compound, particularly NaHCO3If the sides A- or the sides A- one kind or
Suspension in dry kind of component, and
M5) make in step m4) in formed the suspension contacted with the composition comprising at least one isocyanates to make
Standby polyurethane foam, wherein compound discharge chemistry and/or physical blowing agent and the wherein change under heat and/or chemical activation
Closing object has the size distribution for being expressed as D50 for being equal to or less than 1 μm.
Another aspect of the present invention relates to a kind of as obtained by the method for the present invention as outlined above (modified)
Polyurethane foam.Preferably, the foam includes abscess, these abscesses have the slave 10nm to 1 measured according to ASTM D 3576
μm, the average cell size preferably from 50nm to 500nm, more preferably from 100nm to 250nm.Polyurethane foam according to the present invention
Foam or the polyurethane foam of modification are preferably rigid closed-cell foam.The polyurethane foam or the polyurethane foam of modification can be with
Selected from the flexible or semiflexible foam or skinned foam for example for producing sole or for filling seat cushion.
Preferably, the polyurethane foam or the polyurethane foam of modification are produced by spraying foaming.It is further preferred that this hair
Bright method is used for producing discontinuous or continuous plate, the pipe for pipe insulation, sandwich plate, laminate and blocky bubble
Foam.It is further preferred that the foam of the present invention is eliminated for noise.The further aspect of the present invention is related to a kind of composition, the combination
Object is comprising at least one polyalcohol and can be sent out by the degradation of thermal induction and/or chemical induction to discharge chemistry and/or physics
The compound of infusion, the wherein compound have the size distribution for being expressed as D50 equal to or less than 1 μm;And such combination
Purposes of the object in the preparation of polyurethane foam or the polyurethane foam of modification.
The thermal conductivity of the foam of the present invention can be with operating specification " EN 12667:Thermal performance of
building materials and products[The Re Xingneng ] of construction material and product;" by means of protective heat plate and hot-fluid
It counts to measure.
Following instance is intended to illustrate the present invention in a non limiting manner.
Example:
Example 1:The preparation of polyol blends
30min is continued by 13.5wt%NaHCO at 10000rpm by using PENDRAULIK overhead types dissolvers3
(from Su Wei groups) be dispersed in comprising 16.7gB251,50.0g2412 and 33.3gIn the polyol blends of RN 490.Then, so as to get mixture in ball millSL-
25 (manufacturers of C:VMA-Getzmann GmbH) in use ZrO2 pearl (diameters:It 0.5mm) is subjected to grinding steps at 200 rpm
Continue 12.5h.Then, so that the mixture is subjected to sonication step and continue 1 hour.
NaHCO in the suspension of gained is measured as described above3Size distribution and show D50 be 0.85 μm.
Table 1 shows the D50 values with different milling times and optional sonication (1h) acquisition.
Table 1
Example 1b:The preparation of the sides A- with abrasive solvents
Continue 1 hour at 3,000 rpm by NaHCO by using PENDRAULIK overhead types dissolvers3(come from Su Weiji
Group) be dispersed inContain 40wt%NaHCO in HT55 with provide 10kg3Slurry.By with ZrO2
Pearl ball milling (NetzschRS) suspension is milled 4h.This step obtain the size distribution for being expressed as D50 be from
50nm to 150nm depends on total milling time.Then slurry evaporated on the rotary evaporator and by using
PENDRAULIK overhead types dissolvers continues 30min at 10000rpm and the solid of acquisition is redispersed in comprising 16.7gB251,50.0g2412 and 33.3gIn the polyol blends of RN 490.Later will
The other components of the sides A- are added to this polyalcohol/NaHCO3In mixture.
Example 2:The manufacture of polyurethane foam (PU plates)
Using from example 1 and 1b polyol suspension, using the component as shown in the following table prepare polyurethane
Foam:
The polynary of the 100g prepared in example 1 is stirred in the dixie cup of 500mL using PENDRAULIK overhead types dissolvers
Alcohol mixture and fire retardant.Then, it adds MDI and continues to stir 10s at 2500rpm, mixture seems after this
Uniformly and start bubble occur.After stopping blender, which is poured into 1L dixie cups to allow Foam Expansion and cure
Continue at least one day.The foam of acquisition can be used to prepare discontinuous plate.
Example 3:Injection foaming
By conventional means polyurethane foam (spray foam) is prepared using the component as shown in the following table.
* it is expressed as the weight polyol of parts by weight/100
Example 4:The manufacture of polyisocyanurate foam (PIR plates)
Using from example 1 and 1b polyol suspension, poly- isocyanide is prepared using the component as shown in the following table
Urea acid esters foam:
These polyisocyanurate foams are prepared using 200 MDI indexes.
The more of the 80g prepared in example 1 or 1b are stirred in the dixie cup of 500mL using PENDRAULIK overhead types dissolvers
First alcohol mixture, catalyst, fire retardant and surfactant.Then, it adds MDI and continues to stir 10s at 2500rpm,
Mixture seems uniform and starts bubble occur after this.After stopping blender, which is poured into 1L dixie cups
To allow Foam Expansion and cure to continue at least one day.The foam of acquisition can be used to prepare discontinuous plate.
Claims (15)
1. a kind of method for the polyurethane foam being used to prepare polyurethane foam or modification, this method pass through including wherein compound
The decomposition of thermal induction and/or chemical induction is come the step of discharging chemistry and/or physical blowing agent, wherein the compound has and is equal to
Or the size distribution for being expressed as D50 less than 1 μm, preferably equal to or lower than 500nm, more preferably equal to or less than 250nm.
2. according to the method described in claim 1, wherein, which preferably passes through there is no acidic activator
The decomposition of thermal induction discharges the chemistry and/or physical blowing agent.
3. according to the method described in claim 1, wherein, the compound is more excellent preferably there are acidic activator
The chemistry and/or physical blowing agent are discharged by the decomposition of chemical induction in the case of being selected in there are citric acid and/or formic acid.
4. according to the method in any one of claims 1 to 3, wherein the compound is inorganic carbonate, preferably the change
It is NaHCO to close object3。
5. according to the method in any one of claims 1 to 3, wherein the compound is the hydrate of inorganic salts, preferably
The compound is the hydrate of sodium sulphate, and the more preferably compound is Na2SO4·10H2O。
6. the method according to any one of claims 1 to 5, wherein, which has equal to or more than 10nm, preferably
Equal to or more than the size distribution for being expressed as D50 of 50nm, more preferably equal to or greater than 100nm.
7. method according to any one of claim 1 to 6, this approach includes the following steps:
A) suspension for including the compound and at least one polyalcohol is prepared, and
B) suspension formed in step b) is made to be contacted with the composition comprising at least one isocyanates to prepare poly- ammonia
Chemistry and/or physical blowing agent are discharged under heat and/or chemical activation for ester foam, wherein compound and wherein the compound has
There is the size distribution for being expressed as D50 equal to or less than 1 μm.
8. the method for claim 7, this approach includes the following steps:
a1) suspension for including the compound and at least one polyalcohol is prepared,
a2) make in step a1) in formed the suspension reduce the size distribution of the compound through being subject to processing, and
B) make in step a2) in formed the suspension contacted with the composition comprising at least one isocyanates to prepare poly- ammonia
Chemistry and/or physical blowing agent are discharged under heat and/or chemical activation for ester foam, wherein compound and wherein the compound has
There is the size distribution for being expressed as D50 equal to or less than 1 μm.
9. method according to any one of claim 1 to 6, wherein the processing of the reduction size distribution includes that grinding walks
Suddenly, it is preferable to use the grinding steps of ball mill.
10. method according to any one of claim 1 to 6, this approach includes the following steps:M1) prepare includes the change
Close object, particularly NaHCO3With the suspension of abrasive solvents,
M2) make in step m1) in formed the suspension reduce the size distribution of the compound through being subject to processing, especially grind
Step,
M3) by the evaporative removal abrasive solvents,
M4) prepare in step m3) in formed the compound, particularly NaHCO3In the sides A- or in one kind of the sides A- or several
Suspension in component, and
M5) make in step m4) in formed the suspension contacted with the composition comprising at least one isocyanates it is poly- to prepare
Urethane foam, wherein compound discharge chemistry and/or physical blowing agent and the wherein compound under heat and/or chemical activation
With the size distribution for being expressed as D50 equal to or less than 1 μm.
11. according to the method described in claim 10, wherein, the processing of the reduction size distribution includes grinding steps, preferably ball
Grind step.
12. a kind of polyurethane foam or the polyurethane foam of modification, pass through the side as described in any one of claim 1 to 11
Method can get.
13. foam as claimed in claim 12, which includes abscess, these abscesses have to be measured according to ASTM D 3576
Slave 10nm to 1 μm, the average cell size preferably from 50nm to 500nm, more preferably from 100nm to 250nm.
14. a kind of composition, the composition includes at least one polyalcohol and can pass through the drop of thermal induction and/or chemical induction
Solution discharges the compound of chemistry and/or physical blowing agent, and wherein the compound has is expressed as D50 equal to or less than 1 μm
Size distribution.
15. purposes of the composition according to claim 14 in preparing the polyurethane foam of polyurethane foam or modification.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16157615 | 2016-02-26 | ||
| EP16157615.2 | 2016-02-26 | ||
| PCT/EP2017/054302 WO2017144651A1 (en) | 2016-02-26 | 2017-02-24 | Process for the preparation of a polyurethane foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108699209A true CN108699209A (en) | 2018-10-23 |
Family
ID=55527756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780014974.7A Pending CN108699209A (en) | 2016-02-26 | 2017-02-24 | The method for being used to prepare polyurethane foam |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20210189121A1 (en) |
| EP (1) | EP3420008A1 (en) |
| JP (1) | JP2019507818A (en) |
| KR (1) | KR20180114183A (en) |
| CN (1) | CN108699209A (en) |
| CA (1) | CA3014705A1 (en) |
| RU (1) | RU2018133695A (en) |
| SG (1) | SG11201806874QA (en) |
| WO (1) | WO2017144651A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019063562A1 (en) * | 2017-09-27 | 2019-04-04 | Solvay Sa | Process for the preparation of polyurethane foam |
| WO2019117292A1 (en) * | 2017-12-15 | 2019-06-20 | 株式会社イノアックコーポレーション | Method for producing polyurethane foam |
| CN110396212A (en) * | 2018-04-25 | 2019-11-01 | 北京市建筑工程研究院有限责任公司 | A kind of hard polyurethane foams auxiliary blowing agent |
| JP7212433B2 (en) * | 2019-04-26 | 2023-01-25 | 株式会社イノアックコーポレーション | Polyurethane foam and its manufacturing method |
| US11267945B2 (en) | 2020-01-31 | 2022-03-08 | Ddp Specialty Electronic Materials Us, Llc | Flame-retardant polyurethane foam |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3455848A (en) * | 1964-05-05 | 1969-07-15 | Ncr Co | Polyurethane foam-producing compositions comprising microencapsulated particles and a method of making foams therefrom |
| US3933548A (en) * | 1974-08-19 | 1976-01-20 | Beatrice Foods Co. | Production of urethane foams and laminates thereof |
| CN1727376A (en) * | 2004-07-28 | 2006-02-01 | 井上株式会社 | Process for producing flexible polyurethane foam using hydrated metal salt blowing agents |
| WO2007100502A1 (en) * | 2006-02-22 | 2007-09-07 | Dow Global Technologies, Inc. | One-component flexible polyurethane foam compositions and methods for their use |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5424077A (en) | 1993-07-13 | 1995-06-13 | Church & Dwight Co., Inc. | Co-micronized bicarbonate salt compositions |
| JP4410665B2 (en) * | 2004-07-28 | 2010-02-03 | 株式会社イノアックコーポレーション | Method for producing flexible polyurethane foam |
| DE102009053218A1 (en) | 2009-11-06 | 2011-07-14 | Bayer MaterialScience AG, 51373 | Process for producing a polyurethane foam by means of supercritical or near-critical blowing agent |
-
2017
- 2017-02-24 CN CN201780014974.7A patent/CN108699209A/en active Pending
- 2017-02-24 US US16/077,824 patent/US20210189121A1/en not_active Abandoned
- 2017-02-24 EP EP17707277.4A patent/EP3420008A1/en not_active Withdrawn
- 2017-02-24 SG SG11201806874QA patent/SG11201806874QA/en unknown
- 2017-02-24 JP JP2018544914A patent/JP2019507818A/en active Pending
- 2017-02-24 RU RU2018133695A patent/RU2018133695A/en not_active Application Discontinuation
- 2017-02-24 WO PCT/EP2017/054302 patent/WO2017144651A1/en active Application Filing
- 2017-02-24 KR KR1020187027174A patent/KR20180114183A/en not_active Withdrawn
- 2017-02-24 CA CA3014705A patent/CA3014705A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3455848A (en) * | 1964-05-05 | 1969-07-15 | Ncr Co | Polyurethane foam-producing compositions comprising microencapsulated particles and a method of making foams therefrom |
| US3933548A (en) * | 1974-08-19 | 1976-01-20 | Beatrice Foods Co. | Production of urethane foams and laminates thereof |
| CN1727376A (en) * | 2004-07-28 | 2006-02-01 | 井上株式会社 | Process for producing flexible polyurethane foam using hydrated metal salt blowing agents |
| WO2007100502A1 (en) * | 2006-02-22 | 2007-09-07 | Dow Global Technologies, Inc. | One-component flexible polyurethane foam compositions and methods for their use |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20180114183A (en) | 2018-10-17 |
| SG11201806874QA (en) | 2018-09-27 |
| RU2018133695A (en) | 2020-03-26 |
| US20210189121A1 (en) | 2021-06-24 |
| CA3014705A1 (en) | 2017-08-31 |
| EP3420008A1 (en) | 2019-01-02 |
| WO2017144651A1 (en) | 2017-08-31 |
| JP2019507818A (en) | 2019-03-22 |
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